CN106062594B - Polarizing film, the manufacturing method of polarizing film and liquid crystal display device - Google Patents

Abstract

It is an object of the present invention to provide the visual reduced polarizing films that can inhibit liquid crystal display device.Polarizing film of the invention contains polarizer, it is configured at the protective film A of the one side of above-mentioned polarizer, with the protective film B for the another side for being configured at above-mentioned polarizer, at least the above protective film A is Nian Jie with above-mentioned polarizer via active energy ray-curable adhesive layer, said protection film A contains cellulose esters and petchem, and the content of above-mentioned petchem is 5~30 mass % relative to above-mentioned cellulose esters, after said protection film A is saved 100 hours at 80 DEG C of 90%RH, the size changing rate (%) of the longitudinal direction α of film is set as A (α), when the size changing rate (%) of orthogonal to that short side direction β is set as A (β), meet -1.5≤A (α)≤- 0.3, -1.5≤A (β)≤- 0.3.

Description

Polarizing film, the manufacturing method of polarizing film and liquid crystal display device

Technical field

The present invention relates to polarizing film, the manufacturing method of polarizing film and liquid crystal display devices.

Background technique

In recent years, needs of the liquid crystal display device as the liquid crystal display of the portable equipments such as smart phone, tablet terminal Increasing.Such small-sized liquid crystal display device 1 contains the liquid crystal cells for being for example equipped with the IPS mode of touch panel module 3 and clamp its a pair of of polarizing film 5 and 7 (referring to Fig. 3).Polarizing film 5 is matched containing polarizer 5-1, in the face of its liquid crystal cell side The protective film 5-3B (F1) of the face configuration of the protective film 5-3A (F2), He Qi opposite side that set.Similarly, polarizing film 7 contains Polariscope 7-1, the protective film 7- configured in the protective film 7-3A (F3) of the face of its liquid crystal cell side configuration, the face of He Qi opposite side 3B(F4)。

As polarizing film, it is known that for example containing polarizer and as clamp its protective film two cellulose ester membranes, make Wherein liquid crystal cell side configuration cellulose ester membrane become meet 0nm≤Re (630)≤20nm, | Rth (630) |≤25nm's Polarizing film of film etc. (such as patent document 1).It shows in the publication: display caused by the variation in order to inhibit humidity, temperature Unevenness reduces the size changing rate of cellulose ester membrane configured in liquid crystal cell side as far as possible, specifically make its 0.5% with Under.

Such polarizing film is usually by viscous with polyethenol series bonding agent (water paste) etc. by polarizer and cellulose ester membrane It connects and obtains (such as patent document 1).Recently, water need not be used from the manufacturing process of polarizing film, it can be good with the short time Ground bonding etc. considers, substitutes polyethenol series bonding agent (water paste) sometimes and uses active energy ray-curable bonding agent.

Existing technical literature

Patent document

Patent document 1: Japanese Unexamined Patent Publication 2008-217022 bulletin

Summary of the invention

Subject to be solved by the invention

But previous make protective film and polarizer via active energy line curing with regard to such shown in patent document 1 Type bonding agent and for the polarizing film that has been bonded, exist be easy to happen liquid crystal display device display it is uneven, visual be easy drop Low such problems.The problem is especially significant in small-sized liquid crystal display device.

The reasons why visuality reduces is not necessarily clear, but thinks as described below.That is, if the inside of liquid crystal display device 1 As high temperature and humidity, polarizer 5-1,7-1, particularly polarizer 7-1 are easy significantly change in size (contraction)；Liquid crystal cells 3 glass substrate is not easy change in size.Moreover, if will configure between polarizer 7-1 and the glass substrate of liquid crystal cells 3 Protective film 7-3A (F3) is Nian Jie with active energy ray-curable bonding agent with polarizer 7-1, then compared with previous water paste, bonding Power is secured, therefore the convergent force of polarizer 7-1 is transmitted as readily to protective film 7-3A (F3).At this point, if protective film 7-3A (F3) Size changing rate it is small, relatively become larger to protective film 7-3A (F3) convergent force of polarizer 7-1 applied, in protective film 7-3A (F3) deformation is easy to produce in.If generating such deformation, it is believed that be easy to produce deformation (birefringent) optically, be easy to produce The display of raw display device is uneven.

For small-sized liquid crystal display device, it is exposed to due to use condition under hot environment, high humidity environment.Separately Outside, small-sized liquid crystal display device is not only also containing the rechargeable battery as heat source, but also device volume is also small.As a result, especially It is when charging, under high temperature or high humidity environment in use, heat, moisture are easy to accumulate in the device, there is deformation optically It is particularly easy to the tendency occurred.

The present invention is completed in view of above-mentioned actual conditions, and it is an object of the present invention to provide polarizing film below: its be by polarizer with The polarizing film that protective film has been bonded via active energy ray-curable adhesive layer, can inhibit the visuality of liquid crystal display device Reduction.

Means for solving the problems

[1] polarizing film is polarized containing polarizer, in the protective film A of above-mentioned polarizer being configured on one side and above-mentioned The protective film B, at least the above protective film A that the another side of mirror is configured with via active energy ray-curable bonding agent solidified material layer Nian Jie with above-mentioned polarizer, said protection film A contains cellulose esters and glycol and dicarboxylic acids is made to carry out polyester obtained from polycondensation Compound, and the content of above-mentioned petchem is 5~30 mass % relative to above-mentioned cellulose esters, and said protection film A is existed After saving 100 hours under 80 DEG C of 90%RH, the longitudinal direction α of film size changing rate (%) is set as A (α), will be with above-mentioned length When the size changing rate (%) of edge direction α orthogonal short side direction β is set as A (β), said protection film A meet following formula (1) and (2)。

-1.5≤A(α)≤-0.3…(1)

-1.5≤A(β)≤-0.3…(2)

[2] polarizing film described in [1], wherein above-mentioned petchem is to make selected from by aliphatic dicarboxylic acid and ester ring type Dicarboxylic acids composition group in dicarboxylic acids in the group being made of aliphatic diol, the pure and mild ester ring type glycol of alkyl ether two Glycol carries out compound obtained from polycondensation.

[3] polarizing film described in [1] or [2], wherein said protection film A meets following formula (3) and (4).

- 1.5≤A (α) < -0.5 ... (3)

- 1.5≤A (β) < -0.5 ... (4)

[4] described in any item polarizing films of [1]~[3], wherein said protection film B is via active energy ray-curable The solidified material layer of bonding agent and it is Nian Jie with above-mentioned polarizer, after said protection film B is saved 100 hours at 80 DEG C of 90%RH , the size changing rate (%) of the longitudinal direction α of film be set as B (α), by the short side direction β orthogonal relative to above-mentioned longitudinal direction α Size changing rate (%) when being set as B (β), said protection film A and B meet following formula (5) and (6).

|A(α)-B(α)|≤0.4…(5)

|A(β)-B(β)|≤0.4…(6)

[5] described in any item polarizing films of [1]~[4], wherein above-mentioned polarizer with a thickness of 3~15 μm.

[6] described in any item polarizing films of [1]~[5], wherein will defined by following formula (I)s and measure wave The delay in direction is set as Ro (590) in the face measured under long 590nm, will be defined by following formula (II)s and in measurement wavelength When the delay of the thickness direction measured under 590nm is set as (590) Rth, said protection film A meets | Ro (590) |≤10nm, | Rth (590)|≤10nm。

Formula (I) Ro=(nx-ny) × t (nm)

Formula (II) Rth={ (nx+ny)/2-nz } × t (nm)

(in formula (I) and (II), nx indicates that direction refractive index is as the refraction on maximum slow axis direction x in the face of film Rate；Ny indicates the refractive index on the direction y that direction is orthogonal with above-mentioned slow axis direction x in the face of film；The thickness side of nz expression film Refractive index on z；The thickness of t (nm) expression film)

[7] described in any item polarizing films of [1]~[6], wherein said protection film A also contains lubricant.

[8] described in any item polarizing films of [1]~[7], wherein said protection film B also contains high rigidity agent.

[9] described in any item polarizing films of [1]~[8], wherein said protection film A with a thickness of 10~60 μm.

[10] described in any item polarizing films of [1]~[9], wherein become the side of liquid crystal cell side with said protection film A Formula is configured and is used.

[11] manufacturing method of polarizing film is the manufacturing method of described in any item polarizing films of [1]~[10], includes: 1) prepare the process of protective film A；2) process for obtaining sandwich, the sandwich contain polarizer, in the one side of above-mentioned polarizer The said protection film A that has been laminated via active energy ray-curable adhesive layer and above-mentioned polarizer another side via work The protective film B that property energy-line solidifying type adhesive layer is configured with；With 3) to above-mentioned sandwich irradiation active energy ray, make above-mentioned work Property energy-line solidifying type adhesive layer solidifies the process for obtaining polarizing film；The above-mentioned process for 1) preparing protective film A includes: 1A) It obtains containing cellulose esters and glycol and dicarboxylic acids is made to carry out petchem and above-mentioned polyester chemical combination obtained from polycondensation Process of the content of object relative to the membranoid substance that above-mentioned cellulose esters is 5~30 mass %；1B) by above-mentioned membranoid substance 110~ The process stretched at a temperature of 135 DEG C, with 1.03~1.06 times of stretching ratio in width direction；1C) by above-mentioned stretching Obtained membrane edge with the tension of 70~80N/m conveying side 100~120 DEG C at a temperature of make it dry 5~10 minutes process.

[12] liquid crystal display device successively contains the first polarizing film, liquid crystal cells, the second polarizing film and backlight, above-mentioned Second polarizing film is described in any item polarizing films of [1]~[10], and the protective film A of above-mentioned second polarizing film is configured above-mentioned On liquid crystal cells or both above-mentioned first polarizing film and above-mentioned second polarizing film are the described in any item of [1]~[10] The protective film A of the protective film A of above-mentioned first polarizing film and above-mentioned second polarizing film are arranged respectively at above-mentioned liquid crystal list by polarizing film In member.

[13] liquid crystal display device described in [12], wherein above-mentioned liquid crystal cells are the liquid crystal of IPS mode or FFS mode Unit.

[14] it is 6 inches below that liquid crystal display device described in [12] or [13], which is the length containing diagonal direction, The small-sized liquid crystal display device of display unit and rechargeable battery.

The effect of invention

According to the present invention it is possible to provide polarizing film below: it is to consolidate polarizer and protective film via active energy ray Change type adhesive layer and the polarizing film being bonded, can inhibit liquid crystal display device visual reduction, particularly small-sized liquid crystal The visual reduction of display device.

Detailed description of the invention

Fig. 1 is the figure for indicating an example of composition of polarizing film of the invention.

Fig. 2 is the schematic diagram for indicating an example of small-sized liquid crystal display device.

Fig. 3 is the schematic diagram for indicating an example of basic composition of liquid crystal display device.

Specific embodiment

1. polarizing film

Polarizing film of the invention contains polarizer, the protective film A in the configuration of its one side and the protective film in another side configuration B。

Fig. 1 is the figure for indicating an example of composition of polarizing film of the invention.As shown in fig. 1, polarizing film 10 of the invention Protective film 13A (protective film A) containing polarizer 11, in the configuration of its one side and the protective film 13B (protection in another side configuration Film B).Protective film 13A and 13B respectively via the solidified material layer 15 and 15 of active energy ray-curable bonding agent and with polarizer 11 Bonding.In protective film 13A and 13B, preferably by protective film 13A configuration on the liquid crystal cells of aftermentioned display device.

1-1. polarizer 11

Polarizer 11 is the element for only passing through the light of the plane of polarization of certain orientation, it is now known that representative polarizer For polyethenol series polarizing coating.There is the polarizing coating for dyeing iodine to polyvinyl alcohol mesentery in polyethenol series polarizing coating and makes two colors The polarizing coating that property dyestuff dyes polyvinyl alcohol mesentery.

Polyethenol series polarizing coating can be polyvinyl alcohol mesentery is uniaxially stretched after dyed with iodine or dichroic dye Film (preferably further with boron compound implement durability processing film)；Be also possible to polyvinyl alcohol mesentery iodine or The film (film of durability processing is preferably further implemented with boron compound) being uniaxially stretched after dichroic dye dyeing.

For the thickness of polarizer 11, from polarizing film being not only thinned, but also can reduce heat, humidity causes Convergent force etc. consider, preferably 2~30 μm, more preferably 3~15 μm.

As described above, polarizer is be bonded via the solidified material layer of active energy ray-curable bonding agent with protective film When, if size changing rate caused by the heat of the protective film configured between polarizer and liquid crystal cells, humidity is small, it is easy to produce The display of raw display device is uneven (visual reduction).In this regard, the inventors discovered that by making in polarizer and liquid crystal list The size changing rate of the protective film 13A (protective film A) configured between member moderately becomes larger, and can inhibit the display in display device Uneven (visual reduction).

Its reason is not necessarily clear, but thinks as described below.By make the glass substrate of polarizer and liquid crystal cells it Between the size changing rate of protective film 13A (protective film A) that configures be that the convergent force of protective film 13A can be made to become larger more than certain. As a result, the convergent force to the protective film 13A polarizer 11 applied can be made relatively to become smaller, can make to produce in protective film 13A Raw deformation reduces.Think it is possible thereby to reduce the deformation (birefringent) optically of protective film 13A, it is possible to reduce display is not .

That is, in the present invention, by the protective film 13A configured between polarizer and liquid crystal cells, protect under 80 DEG C of 90%RH The size changing rate (%) of after having deposited 100 hours, film longitudinal direction α is set as A (α), by the short side orthogonal with longitudinal direction α When the size changing rate (%) of direction β is set as A (β), preferably protective film A meets following formula (1) and (2).

-1.5≤A(α)≤-0.3…(1)

-1.5≤A(β)≤-0.3…(2)

In order to further decrease the deformation generated in protective film 13A, more preferable protective film 13A meet following formula (3) and (4)。

- 1.5≤A (α) < -0.5 ... (3)

- 1.5≤A (β) < -0.5 ... (4)

The size changing rate of so-called film, indicate saved 100 hours at 80 DEG C of 90%RH after film, relative to preservation before Film size changing amount ratio.The longitudinal direction α of protective film 13A indicates the length in the scroll of the polarizing film of long size shape Direction (direction MD) or orthogonal to that direction (direction TD)；Preferably indicate direction (direction TD) orthogonal to the longitudinal direction. In the case where piece leaf film (piece leaf Off ィ Le system) that protective film 13A is square, the longitudinal direction α of protective film 13A can be orthogonal Two sides in it is arbitrary any one.The length direction (direction MD) and the absorption axis direction of polarizer of polarizing film are orthogonal or consistent, It is preferably consistent with the absorption axis direction of polarizer.

In order to make the size changing rate above range of protective film 13A, the fiber for constituting protective film 13A is preferably for example reduced The orientation of plain ester molecule.The orientation of cellulose esters molecule can by the composition and manufacturing condition of protective film A (stretching condition, Drying condition and transport condition after stretching) it adjusts.In order to improve the size changing rate of protective film 13A, preferably for example 1) make The content of petchem is certain following；2) stretching condition is set as the condition reduced to the tensile stress that film applies；And And 3) reduce conveyance tension, more preferably in addition to it is above-mentioned 1)~3) other than so 4) make stretching after drying condition become to mitigate.

1-2. protective film 13A

For protective film 13A, as described above, directly or via other layers contiguously configured with liquid crystal cells, it can With phase difference regulatory function.Protective film A contains cellulose esters as principal component.

(cellulose esters)

Cellulose esters be make cellulose and carbon atom number 2~22 aliphatic carboxylic acid and aromatic carboxylic acid at least one into Compound obtained from row esterification.

In the example of cellulose esters, contain cellulose triacetate, cellulose diacetate, cellulose propionate, butyric acid fiber Element, cellulose-acetate propionate, cellulose acetate-butyrate, cellulose benzoate, acetic acid cellulose benzoate etc..Wherein, preferred phase The low cellulose esters of showing property of potential difference, preferably cellulose triacetate.

Total degree of substitution of the acyl group of cellulose esters be 2.0~3.0 or so, preferably 2.5~3.0, more preferably 2.7~ 3.0, further preferably 2.8~2.95.In order to reduce showing property of phase difference, total degree of substitution of acyl group is preferably improved.

The carbon atom number of acyl group contained in cellulose esters is preferably 2~7, and more preferably 2~4.From good in order to obtain Heat resistance etc. consider that acyl group contained in cellulose esters preferably comprises acetyl group.The degree of substitution of the acyl group of 3 or more carbon atom number Preferably 0.9 hereinafter, more preferably 0.

The degree of substitution of the acyl group of cellulose esters method specified in ASTM-D817-96 measures.

For the weight average molecular weight of cellulose esters, more than a certain amount of mechanical strength, preferably 5.0 × 10 in order to obtain⁴ ~5.0 × 10⁵, more preferably 1.0 × 10⁵~3.0 × 10⁵, further preferably 1.5 × 10⁵~2.8 × 10⁵.Cellulose esters Molecular weight distribution (weight average molecular weight Mw/ number-average molecular weight Mn) is preferably 1.0~4.5.

The weight average molecular weight and molecular weight distribution of cellulose esters can be measured by gel permeation chromatography (GPC).Measurement strip Part is as described below.

Solvent: methylene chloride

Column: 3 Shodex K806, K805, K803G (Showa electrician (strain) manufacture) connections are used.

Column temperature: 25 DEG C

Sample solution concentration: 0.1 mass %

Detector: RI Model 504 (manufacture of GL Science company)

Pump: L6000 (Hitachi (strain) manufacture)

Flow: 1.0ml/min

Calibration curve: using using standard polystyren STK standard polystyrene (Tosoh (strain) manufacture) Mw= 1.0×10⁶~5.0 × 10²The obtained calibration curve of 13 samples.13 samples preferably select at substantially equal intervals.

(petchem)

For protective film 13A, considers from order to be easy sized change rate, phase difference etc., preferably also contain polyester Compound.

Petchem is that dicarboxylic acids and glycol is made to carry out compound obtained from polycondensation.Dicarboxylic acids can be for selected from aliphatic One or more of dicarboxylic acids, ester ring type dicarboxylic acids and aromatic dicarboxylic acid.Glycol can be for selected from aliphatic diol, alkyl ether One or more of glycol, ester ring type glycol and aromatic diol.Wherein, from being not easy to make phase difference to show and size changing rate Do not become smaller exceedingly etc. and to consider, preferably make dicarboxylic acids in aliphatic dicarboxylic acid and ester ring type dicarboxylic acids with selected from fat Glycol in race's glycol, alkyl ether glycol and ester ring type glycol carries out (the aliphatic poly esterification of petchem obtained from polycondensation Close object).

That is, petchem is preferably indicated by general formula (1) or (2).

General formula (1):

B₁-(G-A-)mG-B₁

The G of general formula (1) indicates the group from aliphatic diol or alkyl ether glycol.The carbon atom number of aliphatic diol is excellent It is selected as 2~12.Contain ethylene glycol, diethylene glycol (DEG), 1,2-PD, 1,3-PD, 1,2- fourth in the example of aliphatic diol Glycol, 1,3-BDO, 1,4-butanediol, 1,5-PD, 1,6- hexylene glycol, 1,5-PD etc., preferably ethylene glycol, 1, 2- propylene glycol, 1,3-PD, 1,2- butanediol, 1,3-BDO, 1,4-butanediol, 1,6- hexylene glycol.

The carbon atom number of alkyl ether glycol is preferably 4~12.Contain diethylene glycol (DEG), three sweet in the example of alkyl ether glycol Alcohol, tetraethylene glycol, dipropylene glycol, tripropylene glycol etc..

The A of general formula (1) indicates the group from aliphatic dicarboxylic acid or ester ring type dicarboxylic acids.The carbon of aliphatic dicarboxylic acid is former Subnumber is preferably 4~12.In the example of aliphatic dicarboxylic acid containing malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, Suberic acid, azelaic acid, decanedioic acid, heneicosane dicarboxylic acid, dodecanedicarboxylic acid etc..

The B of general formula (1)₁Indicate the group from aliphatic monocarboxylic acid or ester ring type monocarboxylic acid.The carbon of aliphatic monocarboxylic acid Atomicity is preferably 1~12.Contain formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, heptan in the example of aliphatic monocarboxylic acid Acid, octanoic acid, n-nonanoic acid, capric acid, 2- ethyl-hexanecarboxylic acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palm Acid, heptadecanoic acid, stearic acid, nonadecanoic acid, arachidic acid, behenic acid, tetracosanoic acid, cerinic acid, carboceric acid, montanic acid, 30 Saturated fatty acid, undecenoic acid, oleic acid, sorbic acid, linoleic acid, linolenic acid, the arachidonic acid of acid, lacceroic acid etc. etc. Unsaturated fatty acid etc. considers, preferably acetic acid from the compatibility with cellulose esters is well equal.

With regard to the B of general formula (1)₁, for G and A, consider from order to be not easy to make phase difference to show etc., be preferably all free of aromatic rings. M expression repeat number, preferably 1 or more 170 or less.

In the example of the petchem indicated by general formula (1), contain compound shown in table 1.

[table 1]

General formula (2):

B₂-(A-G-)nA-B₂

The G and A of general formula (2) are defined in the same manner as the G and A of general formula (1) respectively.The B of general formula (2)₂It indicates to come from aliphatic The group of monohydric alcohol or ester ring type monohydric alcohol.The carbon atom number of aliphatic monobasic alcohol is preferably 1~12.The example of aliphatic monobasic alcohol Contain methanol, ethyl alcohol, propyl alcohol, isopropanol etc. in son；Contain cyclohexanol etc. in the example of ester ring type monohydric alcohol.

With regard to the B of general formula (2)₂, G and A, consider from order to be not easy to make phase difference to show etc., be preferably all free of aromatic rings.N table Show repeat number, preferably 1 or more 170 or less.

Contain compound shown in table 2 in the example of the petchem indicated as general formula (2).

[table 2]

	B2	G	A	Mw
					K10	CH3O	C2H4-O	CO-COO	400
K11	C2H5O	C2H4-O	CO-C2H4-COO	1000
					K12	C2H5O	C4H8-O	CO-COO	2000
K13	C2H5O	C2H4-O	CO-COO	10000

For the weight average molecular weight Mw of petchem, from make with the compatibility of cellulose esters it is good from the viewpoint of, Preferably 20000 hereinafter, more preferably 5000 hereinafter, most preferably 3000 or less.On the other hand, from the polyester inhibited in film From the viewpoint of volatilization of compound etc., the weight average molecular weight Mw of petchem can for 400 or more, preferably 700 or more, most Preferably 1000 or more.

For the content of petchem, from the plastic effect of film, obtain preferred phase difference from the viewpoint of, relatively In cellulose esters, preferably 1~40 mass %, more preferably 5~30 mass %, further preferably 5~20 mass % are optimal It is selected as 10~18 mass %.

For by general formula (1) or the petchem of (2) expression, due to making fiber compared with aromatic polyester compound The effect of plain ester molecule orientation is small, therefore the size changing rate as caused by heat, humidity of protective film 13A is not easy exceedingly to become smaller. In addition, preferably reducing the phase difference, particularly Rth of protective film 13A by the petchem that general formula (1) or (2) indicate.

It, as needed can be further containing removing auxiliary agent, ultraviolet absorbing agent, for assigning cunning for protective film 13A The various of the delustering agent (particle) of dynamic property, lubricant, aftermentioned high rigidity agent, impact supporting material for improving toughness etc. add Add agent.

(ultraviolet absorbing agent)

Ultraviolet absorbing agent can be benzotriazole based compound, 2- dihydroxy benaophenonel based compound or phenyl salicylate Based compound etc..Specifically, 2- (5- methyl -2- hydroxy phenyl) benzotriazole, 2- [2- hydroxyl -3,5- bis- (α, α-can be enumerated Dimethyl benzyl) phenyl] triazole types, 2- such as -2H- benzotriazole, 2- (3,5- di-tert-butyl-2-hydroxy phenyl) benzotriazole Hydroxyl -4- methoxy benzophenone, 2- hydroxyl -4- octyloxybenzophenone, 2,2 '-dihydroxy -4- methoxy benzophenones etc. Benzophenone.

Ultraviolet absorbing agent can be commercially available product, the チ ヌ ビ Application 109 containing the manufacture of BASF Japanese firm, チ in example The チ ヌ ビ such as ヌ ビ Application 171, チ ヌ ビ Application 234, チ ヌ ビ Application 326, チ ヌ ビ Application 327, チ ヌ ビ Application 328, チ ヌ ビ Application 928 Application series or 2,2 '-di-2-ethylhexylphosphine oxides [6- (2H- benzotriazole -2- base) -4- (1,1,3,3- tetramethyl butyl) phenol] (point Son amount 659；As the example of commercially available product, the LA31 for thering is Asahi Denka Co., Ltd. to manufacture) etc..

Protective film configuration (is made in the case where the face of the liquid crystal cell side of polarizer as aftermentioned protective film F2 or F3 In the case where), ultraviolet screener is not required, the content of ultraviolet absorbing agent relative to cellulose esters, can be set as 0~ 0.5 mass % or so.On the other hand, protective film configuration (is made in the case where the face of the opposite side of the liquid crystal cells of polarizer In the case where for aftermentioned protective film F1 or F4 use), the content of ultraviolet screener is relative to cellulose esters, with mass ratio table Show, 1ppm~5.0% or so, preferably 0.5~3.0% or so can be set as.

(lubricant)

Protective film 13A preferably also contains lubricant.For protective film 13A, in order to make change in size caused by heat, humidity Rate is to be manufactured more than certain with low conveyance tension.But if reducing conveyance tension, protective film and conveying roller occurs Poor contact is easy to cause to damage to the surface of protective film, and mist degree is easy to increase.Therefore, lubrication is also contained by protective film 13A Agent can inhibit the poor contact with roller, inhibit the increase of its caused mist degree.

Lubricant can be polysiloxane, the higher fatty acids, height of dimethyl silicone polymer, polydiethylsiloxane etc. Grade aliphatic alcohol, high fatty acid amide, higher fatty acid metal salt, higher fatty acids and ester of senior aliphat alcohol etc..These In, preferably by the compound of the following general formula (3) expression.

[changing 1]

R₁-L-R₂…(3)

The L of general formula (3) indicate at least containing ester bond (- C (=O) O-), amido bond (- C (=O) NH-) or carbonyl (- C (= O) -) divalent group.These carbonyls can assign the compound indicated by general formula (3) good affine with cellulose esters Property.Specifically, L indicates ester bond, amido bond, carbonyl or " by ester bond, amido bond or carbonyl and is selected from alkylidene, nitrogen-atoms, oxygen The group of the combined divalent of one or more of atom, sulphur atom, zinc atom, calcium atom and magnesium atom "；From be easy to get with it is fine The good compatibility for tieing up element ester considers, preferably indicates " by ester bond, amido bond or carbonyl and selected from alkylidene, nitrogen-atoms, oxygen original The group of the combined divalent of one or more of son, sulphur atom, zinc atom, calcium atom and magnesium atom ".

" by ester bond, amido bond or carbonyl and it is being selected from alkylidene, nitrogen-atoms, oxygen atom, sulphur atom, zinc atom, calcium atom Contain in the example of the group of combined divalent with one or more of magnesium atom "

- C (=O)-O-R₃- O-C (=O)-,-C (=O)-NH-R₃- NH-C (=O)-(R₃For the alkylidene of carbon number 1~5)；

- C (=O)-O-M-O-C (=O)-(M is zinc atom, calcium atom or magnesium atom)；

- C (=O)-R₄-O-R₄- C (=O)-,-C (=O)-R₄-S-R₄- C (=O)-,-C (=O)-R₄-NH-R₄- C (= O)-(R₄For the alkylidene of carbon number 1~5)；With

- C (=O)-R₅- C (=O)-(R₅For the alkylidene of carbon number 1~5) etc..

The R of general formula (3)₁Indicate that the alkyl below of carbon atom number 8 or more and 26 or carbon atom number 8 or more and 26 are below Alkenyl.For the carbon atom number of alkyl and alkenyl, consider from good sliding property is easy to get, more preferably 10 or more and 26 Below.Alkyl and alkenyl can be straight-chain, or branch-like considers, preferably from good sliding property is easy to get Straight-chain.

The R of general formula (3)₂Indicate hydrogen atom, the alkyl below of carbon atom number 8 or more and 26 or carbon atom number 8 or more and 26 Alkenyl below；Good sliding property in order to obtain, the preferably alkyl below of carbon atom number 8 or more and 26 or carbon atom number 8 Above and 26 alkenyls below.The carbon atom number of alkyl and alkenyl considers from good sliding property is easy to get, more preferably 10 Above and 26 or less.Alkyl and alkenyl can be straight-chain, or branch-like is examined from good sliding property is easy to get Consider, preferably straight-chain.

In R₂In the case where hydrogen atom ,-LR₂It can be-C (=O) OH ,-C (=O) NH₂Deng.

With regard to R₁With R₂For, can further have the substituent groups such as OH base as needed.In addition, R₁With R₂Can be mutually the same, It can be different.

Contain compound below in the example of the compound indicated by general formula (3).

[changing 2]

[changing 3]

[changing 4]

For the content of lubricant, relative to protective film 13A, preferably 0.05~5 mass %, more preferably 0.1~3 Quality %.If the content of lubricant is more than certain, the sliding property of film when being film-made is improved, and be can inhibit and is damaged to film surface The increase of caused mist degree.If the content of lubricant is certain following, it is possible to produce exudation.

(delustering agent)

Delustering agent can assign sliding property to protective film 13A.Delustering agent can for by the film not damaged the transparency, have The particle that the inorganic compound or organic compound of heat resistance in film making process are constituted.

In the example of inorganic compound for constituting delustering agent, contain silica (silica), titanium dioxide, oxidation Aluminium, zirconium oxide, calcium carbonate, calcium carbonate, talcum, clay, firing kaolin, firing calcium silicates, afwillite, alumina silicate, silicon Sour magnesium and calcium phosphate etc..Wherein, preferably silica, zirconium oxide, in order to enable to the increase of mist degree of film become smaller, more preferably For silica.

In the concrete example of silica, contain ア エ ロ ジ Le 200V, ア エ ロ ジ Le R972V, ア エ ロ ジ Le R972, R974, R812,200,300, R202, OX50, TT600, NAX50 (the above are the manufactures of Japanese ア エ ロ ジ Le (strain)), シ (the above are Nippon Shokubai Co., Ltds by ー ホ ス タ ー KEP-10, シ ー ホ ス タ ー KEP-30, シ ー ホ ス タ ー KEP-50 Manufacture), サ イ ロ ホ ー ビ ッ Network 100 (Fuji シ リ シ ア manufacture), ニ ッ プ シ ー Le E220A (Japanese シ リ カ industry system Make), ア De マ Off ァ イ Application SO (ア De マ テ ッ Network ス manufacture) etc..

The shape of particle of delustering agent be it is unsetting, needle-shaped, flat or spherical, be easy to become good from the transparency of obtained film Good aspect etc. considers, may preferably be spherical.

One kind can be used in delustering agent, by two kinds or more and can also be used to use.In addition, by by partial size, shape (such as It is needle-shaped and spherical etc.) different particles is used in combination, it can highly have both the transparency and sliding property.

For the size of the particle of delustering agent, if the size close to the wavelength of visible light, light scattering and it is transparent It reduces, therefore preferably smaller than the wavelength of visible light, more preferably 1/2 or less the wavelength of visible light.But, if particle it is big Small too small, the improvement of sliding property can not show sometimes, therefore the range for being preferably sized to 80~180nm of particle.It is so-called The size of particle means the size of condensate in the case where particle is the condensate of primary particle.It is not spherical in particle In the case where, the size of particle means and the comparable diameter of a circle of its projected area.

For the content of delustering agent, relative to cellulose esters, 0.05~1.0 mass % or so can be set to, preferably It can be set as 0.1~0.8 mass %.

The physical property of protective film 13A

(change in size)

As described above, in order to reduce due to heat, humidity variation and the deformation optically of protective film 13A that generates, It is preferred that size changing rate after being saved under making the high temperature and humidity of protective film 13A centainly more than.Specifically, by protective film 13A 80 DEG C of 90%RH under save 100 hours after, the size changing rate (%) of the longitudinal direction α of film be set as A (α), will be opposite When the size changing rate (%) of longitudinal direction α orthogonal short side direction β is set as A (β), preferably protective film A meets following formula (1) (2).

-1.5≤A(α)≤-0.3…(1)

-1.5≤A(β)≤-0.3…(2)

Consider from can further make the deformation generated in protective film 13A reduce, protective film 13A more preferably meets following formula (3) and (4).

- 1.5≤A (α) < -0.5 ... (3)

- 1.5≤A (β) < -0.5 ... (4)

The size changing rate of protective film 13A can be measured with the following method.

1) protective film 13A is cut out into 10 × 10cm²Size and sample film is made.The sample film the direction TD (such as Direction α) it is marked in 2 points for leaving 100mm.Similarly, in MD direction (direction β) In orthogonal with the direction TD of sample film 2 points for leaving 100mm mark.After the film has been stood 24 hours at 23 DEG C of 55%RH, each all directions are surveyed respectively Distance D0 between 2 points fixed.

2) then, sample film is saved 100 hours in the baking oven of 80 DEG C of 90%RH.Then, by sample film from baking oven It takes out, the distance D1 at 23 DEG C after 55%RH relative humidity 24 hours, between all directions measures stamped and marked 2 points respectively.

3) then, for each all directions by it is above-mentioned 1) in the D0 that determines and it is above-mentioned 2) under the D1 that determines substitutes into Formula is stated, is calculated size changing rate (%).Value, which becomes negative, indicates that film is shunk.

Size changing rate (%)=(D1-D0)/D0 × 100

As described above, in order to make the size changing rate of protective film 13A it is certain more than, preferably for example 1) make polyester chemical combination The content of object (compound preferably indicated by general formula (1) or (2)) is certain following；2) become stretching condition to apply film Tensile stress reduce condition；And 3) reduce conveyance tension；More preferably in addition to it is above-mentioned 1)~3) other than further 4) make to draw Drying condition after stretching mitigates.

Specifically, in order to improve protective film 13A the direction MD (preferably short side direction β) size changing rate, preferably contain There is the petchem of specified amount, and keeps the conveyance tension of film certain following；The further preferably polyester chemical combination of specified amount Object, and make the conveyance tension of film, stretch back and carry out the complete of drying temperature and drying time of the roller conveying side when making it dry Portion is certain following.In order to improve protective film 13A the direction TD (preferably short side direction β) size changing rate, preferably comprise The petchem of specified amount, and keep draft temperature certain following；The further preferably petchem of specified amount, and It is certain following for making both draft temperature and stretching ratio.

(delay)

The delay R in direction in protective film 13A, the face that is measured under conditions of measuring wavelength 590nm, 23 DEG C of 55%RH₀ Preferably -20nm or more and 20nm are hereinafter, be more preferably -10nm or more and 10nm or less.Protective film 13A, measurement wavelength The delay Rth of the thickness direction measured under conditions of 590nm, 23 DEG C of 55%RH is preferably -20nm or more and 20nm hereinafter, more excellent It is selected as -10nm or more and 10nm or less.The liquid crystal of such as IPS mode is suitable as with the protective film 13A of such length of delay Phase difference protective film (F2 or F3) of display device etc..

Postpone R₀It is defined respectively by formula below with Rth.

Formula (I): R₀=(nx-ny) × d (nm)

Formula (II): Rth={ (nx+ny)/2-nz } × d (nm)

(in formula (I) and (II),

Nx indicates that direction refractive index is as the refractive index on maximum slow axis direction x in the face of film；

Ny indicates the refractive index on the direction y that direction is orthogonal with above-mentioned slow axis direction x in the face of film；

Nz indicates the refractive index on the thickness direction z of film；

The thickness of d (nm) expression film)

Postpone R₀It can be found out for example, by the following method with Rth.

1) damping is carried out to protective film 13A at 23 DEG C of 55%RH.The protection after damping is measured using Abbe refractometer etc. The mean refractive index of film 13A.

2) measuring (strain) measurement with KOBRA21ADH, prince makes to measure wavelength 590nm with the normal parallel of the film surface R of light when being incident on the protective film 13A after damping₀。

3) use KOBRA21ADH measurement using the slow axis in the face of protective film 13A as sloping shaft (rotary shaft), relative to The normal to a surface of the film makes the length of delay R (θ) when measuring the light incidence of wavelength 590nm from the angle (incidence angle (θ)) of θ.Prolong Every 10 ° of 6 points of the progress of the range that the measurement of slow value R (θ) can be 0 °~50 ° in θ.Slow axis refers to guarantor in the face of protective film 13A Middle refractive index becomes maximum axis in the film surface of cuticula 13A, can be confirmed by KOBRA21ADH.

4) R by determining₀And R (θ) and mean refractive index above-mentioned and film thickness, by KOBRA21ADH calculate nx, Ny and nz calculates the Rth under measurement wavelength 590nm.The measurement of delay can carry out under the conditions of 23 DEG C of 55%RH.

(mist degree)

The mist degree of protective film 13A be preferably 1.0% hereinafter, more preferably 0.5% hereinafter, further preferably 0.3% with Under.The mist degree of protective film 13A is full mist degree, can use haze meter (nephelometer) (model: NDH2000, day according to JISK-7136 This electricity color (strain) manufacture) it measures.

In order to keep mist degree certain hereinafter, it is preferred that such as addition lubricant reduces external mist degree.This is because: passing through profit The addition of lubrication prescription can inhibit the poor contact of the film and conveying roller in film, inhibit external mist caused by damaging to film surface The rising of degree.

(thickness)

For the thickness of protective film 13A, consider from order to be thinned polarizing film etc., it is preferably 10~60 μm, more excellent It is selected as 15~45 μm, further preferably 15~30 μm, particularly preferably 15~28 μm.

The manufacturing method of protective film 13A

For protective film 13A, consider from for the failure etc. for reducing striated, it is preferred to use solution casting method (curtain coating) Manufacture.That is, protective film 13A is manufactured preferably through following processes: 1) process for obtaining the rubber cement containing cellulose esters, 2) by the glue Slurry be cast on supporting mass after, make it dry the process for obtaining membranoid substance, 3) obtained membranoid substance is removed from supporting mass Process, 4) make membranoid substance drying and the process stretched and the process for 5) taking obtained film roll.

1) dissolution process

As long as the organic solvent used in the preparation of rubber cement liquid fully dissolves above-mentioned each ingredient of cellulose esters etc., Then can unlimitedly it use.Contain methylene chloride in the example of chlorine-based organic solvent.Contain in the example of chlorine-free organic solvent There are methyl acetate, ethyl acetate, pentyl acetate, acetone, tetrahydrofuran, 1,3-dioxolane, Isosorbide-5-Nitrae-dioxanes, cyclohexanone, first Acetoacetic ester, 2,2,2- trifluoroethanols, 2,2,3,3- hexafluoro -1- propyl alcohol, the fluoro- 2- propyl alcohol of 1,3- bis-, 1,1,1,3,3,3- hexafluoro -2- Methyl-2-propanol, 1,1,1,3,3,3-hexafluoro-2-propanol, 2,2,3,3,3- five fluoro- 1- propyl alcohol, nitroethane etc..Wherein, excellent Select methylene chloride.

In rubber cement, other than above-mentioned organic solvent, the straight chain of the carbon atom number 1~4 of 1~40 mass % is preferably comprised Or the aliphatic alcohol of branch's chain state.By making to contain alcohol in rubber cement liquid, membranoid substance gelation becomes from the removing of metal support It is easy.

As the straight chain of carbon atom number 1~4 or the aliphatic alcohol of branch's chain state, methanol, ethyl alcohol, positive third can be enumerated Alcohol, isopropanol, n-butanol, sec-butyl alcohol, the tert-butyl alcohol.Wherein, from the stability of rubber cement, the also relatively low, drying property of boiling point etc. Consider, preferably methanol, ethyl alcohol.

Cellulose esters etc. dissolved with the method carried out under normal pressure, the method carried out below the boiling point of main solvent, In It more than the boiling point of main solvent pressurizes come the method etc. carried out, pressurizes particularly preferably more than the boiling point of main solvent come the side carried out Method.

2) it is cast process

Rubber cement liquid is passed through into liquid-feeding pump (for example, compression type quantitative gear pump) liquor charging to pressurization die head.Then, from pressurization Rubber cement liquid is cast in the metal support for the annular ad infinitum transferred by the slit of die head (such as stainless steel band or to be revolved The metal drum etc. turned) casting position.

It is preferred that the shape of slit of the mouth mold part of adjustable die head, being easy to make the pressurization die head of uniform film thickness.Compression molding Have rack type die, T-die etc. in head, all it is preferable to use.The surface of metal support becomes mirror surface.

3) solvent evaporates stripping process

The rubber cement liquid being cast in metal support is heated in metal support and steams the solvent in rubber cement liquid Hair, obtains membranoid substance.

In order to evaporate solvent, there are the method from the side-blown air-supply of rubber cement liquid level, the back side from supporting mass to pass by liquid Method, the method conducted heat by radiant heat from surface and the back side etc. of heat, the drying efficiency of rear surface liquid heat-transferring method is good And it is preferred that.It is preferred that making under atmosphere of rubber cement liquid in the range of 40~100 DEG C in metal support, the drying on supporting mass. When in order under the atmosphere in the range of maintaining 40~100 DEG C, preferably the warm wind of the temperature is ejected into metal support Rubber cement liquid level is heated using means such as infrared rays.

Membranoid substance obtained from solvent will be made to evaporate in metal support is removed in removing position.In metal support Temperature at removing position is preferably 10~40 DEG C of range, more preferably 11~30 DEG C of range.

The residual solvent amount of the membranoid substance in metal support when removing can for example be set as the model of 50~120 mass % It encloses.The residual solvent amount of membranoid substance is defined by following formula.

Residual solvent amount (%)=(quality after the heat treatment of quality-membranoid substance before the heat treatment of membranoid substance)/(membranaceous Quality after the heat treatment of object) × 100

Heat treatment when measuring residual solvent amount indicates to carry out heat treatment in 1 hour at 140 DEG C.

In the range of being usually 196~245N/m for metal support and removing tension when film stripping, when removing, is easy In the case where generating fold, is preferably removed with 190N/m tension below, more preferably shelled with 80N/m tension below From.

4) stretching process

The stretching of membranoid substance is preferably in the width direction of film (direction TD), conveying direction (direction MD) or inclined direction At least one party carries out upwards；More preferably carried out in width direction (direction TD).In the width direction (direction TD) of film and conveying side In the case where being stretched to both (direction MD), the stretching of the width direction (direction TD) of film and conveying direction (direction MD) Stretching can successively carry out, can also simultaneously carry out.

As described above, for the stretching of membranoid substance, size changing rate becomes more than a certain amount of protective film in order to obtain 13A is preferably carried out under the condition (stretching ratio, draft temperature) that the tensile stress applied to membranoid substance reduces.Specifically, wide The size changing rate in direction (direction TD) is spent by making the draft temperature one in the stretching process on width direction (direction TD) It is fixed following；Preferably making both draft temperature and stretching ratio is certain hereinafter, so as to moderately improve.

Stretching ratio is preferably set to low, can preferably be set as 1.01~1.06 times in all directions, can more preferably be set as 1.03~1.06 times.In the case where both the width direction (direction TD) of film and conveying direction (direction MD) are stretched, All directions finally can preferably be set as 1.01~1.06 times, can more preferably be set as 1.03~1.06 times.

Draft temperature is it is also preferred that be set as low.Draft temperature when the glass transition temperature of cellulose esters is set as Tg, It can be set as (Tg-40)~(Tg+20) DEG C of range.Specifically, it in the case that the principal component of membranoid substance is cellulose triacetate, draws Stretching temperature is preferably 100~135 DEG C, and more preferably 110~135 DEG C.

Solvent from for the film after stretching fully removes and size changing rate of adjusting film etc. considers, preferably Further make the film dry.The drying of film be preferably used for example in drying device be configured with multiple rollers while by film convey while into Row.

For the drying of film, size changing rate becomes more than a certain amount of protective film 13A in order to obtain, preferably in mitigation Condition carries out under (temperature, time).Specifically, the size changing rate of conveying direction (direction MD) passes through the conveying at least making film Power is certain following；Drying temperature in drying process and drying time after preferably making the conveyance tension of film, stretching is whole To be certain hereinafter, so as to moderately improve.

Drying temperature can preferably be set as 90~125 DEG C, can more preferably be set as 100~120 DEG C, further preferably may be used It is set as 100~115 DEG C.Drying time is also different because of drying temperature, can be set as 5~15 minutes, preferably 5~10 minutes, it is more excellent Selection of land 5~8 minutes.

For the conveyance tension of film, change in size becomes more than a certain amount of protective film 13A in order to obtain, is preferably set to It is low.Specifically, the conveyance tension of film is preferably 50~100N/m, more preferably 70~80N/m.

Therefore, in order to improve width direction (direction TD) and conveying direction (direction MD) the two size changing rate, it is excellent Selection of land make will the membranoid substance containing the petchem of specified amount on width direction (direction TD) stretch when, stretching ratio and Both draft temperatures are certain following；And preferably makes the conveyance tension of film, stretches drying when back carries out roller conveying side drying Temperature and drying time it is all certain following.In particular it is especially preferred that draft temperature is made to become 110~135 DEG C；Make to stretch Multiplying power becomes 1.03~1.06 times；Making the conveyance tension of film becomes 70~80N/m；Drying temperature is set to become 100~120 DEG C；And Become drying time 5~10 minutes.

In the present invention, by making protective film further contain lubricant, the sliding property of film when can be improved film.By This can also inhibit the poor contact of protective film and conveying roller even if reducing conveyance tension, and inhibition causes to damage to the surface of film Wound.As a result, the increase of the mist degree for the protective film 13A that can inhibit.

5) coiling process

Obtained protective film can be provided with long size shape.The protective film of long size shape usually can be on longitudinal direction (direction MD) It batches as web-like and is made and batches body.The length of the protective film of long size shape can be set as the range of 100~10000m.Long size shape The width of protective film can be set as the range of 1~4m, the preferably range of 1.4~3m.

1-3. protective film 13B

To protective film 13B, there is no particular restriction, considers from heat resistance height etc., preferably comprises cellulose esters as principal component. Cellulose esters defines in the same manner as the cellulose esters in protective film 13A, is preferably cellulose triacetate.

Protective film 13B can further contain petchem same as protective film 13A, various additives as needed. In the example of the various additives contained in protective film 13B, not only contain additive same as protective film 13A, but also Also containing high rigidity agent etc..

(high rigidity agent)

High rigidity agent be preferably the polymer for containing the repetitive unit for carrying out the monomer that free the following general formula (4) indicates or by The compound that the following general formula (5)~(8) indicate.These high rigidity agent can be improved the density of protective film 13B and reduce polarizer In boric acid diffusion path.It can inhibit the deterioration of polarizer as a result,.

[changing 5]

General formula (4)

The R of general formula (4)¹Indicate the aliphatic group of hydrogen atom or carbon number 1~4.By R¹The example of the aliphatic group of expression In, contain methyl, ethyl etc..R²Indicate aliphatic group or aromatic group.By R²In the example of the aliphatic group of expression, Contain alkyl, alkenyl, alkynyl, naphthenic base, the preferably alkyl of carbon number 1~6, more preferably methyl, tert-butyl.In aromatic series base Contain phenyl, naphthalene, xenyl, preferably phenyl in the example of group.(A) 5 or 6 yuan of aromatic rings is indicated.Aromatic rings contains not Containing heteroatomic aromatic ring and containing the heteroatomic unsaturated heterocycle of saturation.The integer of n expression 0~4, preferably 0~2, More preferably 0~1.

Polymer containing the repetitive unit for carrying out the monomer that free general formula (4) indicates preferably is by the following general formula (4-1) The copolymer of expression.

[changing 6]

General formula (4-1)

The R of general formula (4-1)²¹、R²²、R²³And R²⁴Each independently represent substituent group.X, y, z is indicated relative in polymer The molar ratio of contained whole repetitive units, x indicate that 1~40%, y indicates that 5~95%, z indicates 1~70%.M1, m2 are respectively Independently indicate 0~4 integer.M3 indicates 0~2 integer.M4 indicates 0~5 integer.R¹⁰¹、R¹⁰²、R¹⁰³Each independently Indicate the aliphatic group of hydrogen atom or carbon number 1~4.

Containing below poly- in the concrete example of the polymer containing the repetitive unit for carrying out the monomer that free general formula (4) indicates Close object.

[changing 7]

The weight average molecular weight of above-mentioned polymer is preferably 200~10000, and more preferably 300~8000, further preferably 400~4000.If above-mentioned weight average molecular weight is that can improve the density of protective film 13B well more than certain.It can press down as a result, The diffusion of the boric acid from polarizer is made, polarizer deterioration is inhibited.If above-mentioned weight average molecular weight be it is certain hereinafter, if not rapid wear The harmful compatibility with cellulose esters.

[changing 8]

General formula (5)

The R of general formula (5)²⁶Indicate aryl；The preferably aryl of carbon number 6~12, more preferably phenyl.R²⁷And R²⁸Respectively solely On the spot indicate hydrogen atom, alkyl or aryl；Preferably hydrogen atom, the alkyl (also containing naphthenic base) of carbon number 1~12 or carbon number 6~ 12 aryl；The more preferably alkyl (also containing naphthenic base) or phenyl of hydrogen atom, carbon number 1~6.R²⁶And R²⁷Can respectively have Substituent group.R²⁶In the example for the substituent group that can have, the alkyl containing halogen atom or carbon number 1~6.R²⁷The substitution that can have Aryl containing carbon number 6~12 in the example of base.

Contain compound below in the concrete example of the compound indicated by general formula (5).

[changing 9]

The weight average molecular weight of the compound indicated by general formula (5) is preferably 200~1000, and more preferably 250~800.

[changing 10]

General formula (6)

The R of general formula (6)¹Indicate hydrogen atom or substituent group.R²Indicate the substituent group indicated by the following general formula (6-1).N1 is indicated 0~4 integer, n1 multiple R when being 2 or more¹Can be mutually the same, it can also be different.N2 indicates that 1~5 integer, n2 are 2 or more When, multiple R²Can be mutually the same, it can also be different.

[changing 11]

General formula (6-1)

The A of general formula (6-1) indicates substituted or unsubstituted aromatic ring.Aromatic ring is preferably phenyl ring.R³And R⁴Respectively solely On the spot indicate hydrogen atom, the alkyl of carbon atom number 1~5 or the substituent group by general formula (6-2) expression.R⁵Indicate singly-bound or carbon atom The alkylidene of number 1~5.X indicates substituted or unsubstituted aromatic ring.Aromatic ring is preferably phenyl ring.N3 indicate 0~10 it is whole Number, when n3 is 2 or more, multiple R⁵Can be mutually the same with X, it can also be different.

[changing 12]

General formula (6-2)

The X of general formula (6-2) indicates substituted or unsubstituted aromatic ring.Aromatic ring is preferably phenyl ring.R⁶~R⁹Respectively solely On the spot indicate the alkyl of hydrogen atom or carbon atom number 1~5.N5 indicates 1~11 integer, when n5 is 2 or more, multiple R⁶~R⁹And X Can be mutually the same, it can also be different.

Contain compound below in the concrete example of the compound indicated by general formula (6).

[changing 13]

The weight average molecular weight of the compound indicated by general formula (6) is preferably 200~1200, and more preferably 250~1000.

[changing 14]

General formula (7)

The R of general formula (7)₁Indicate the substituted or unsubstituted alkyl-carbonyl of formoxyl or carbon atom number 2~15.R₂、R₃、R₄ Each independently represent the alkyl of carbon atom number 1~4.M, n each independently represents 0 or more integer, but is not simultaneously 0.R₁、 R₂、R₃、R₄Have it is multiple in the case where, respectively can be mutually the same, can also be different.

Acyl modified novolak phenolics are also referred to as by the compound that general formula (7) indicate.It is so-called acyl modified, be Refer to that the hydroxyl of novolak phenolics is acylated.The preferred formoxyl of acyl group, carbon atom number 2~15 it is substituted or unsubstituted Alkyl-carbonyl, wherein particularly preferred acetyl group, propiono, bytyry, valeryl.

Contain compound below in the preferred example of the compound indicated by general formula (7).

[changing 15]

[changing 16]

[changing 17]

General formula (8)

The R of general formula (8)₁Indicate nitrogen-atoms or oxygen atom.R₂Expression-COOH or-OH base.R₃Indicate the alkane of carbon number 1~10 Base contains methyl, ethyl etc. in example.R₄Indicate the substituent groups such as the alkyl of carbon number 1~10.

Contain compound below in the concrete example of the compound indicated by general formula (8).

[changing 18]

For the content of the compound indicated by general formula (4)~(8), relative to cellulose esters, it is formed as 0.1~15 Quality %, preferably 0.5~10 mass %, more preferably 0.5~3 mass %.If the content of above compound be centainly with On, the density of film can be fully improved.If the content of above compound is certain hereinafter, can inhibit the rising of exudation, mist degree.

Protective film identical with protective film 13A can be used in protective film 13B.

The physical property of protective film 13B

(size changing rate)

If the size changing rate of protective film 13B and the size changing rate of protective film 13A are significantly different, in polarizing film 10 inside is also deformed, and is easy to happen the curling (warpage) of polarizing film 10.If it happens the curling of such polarizing film 10, The display unevenness being then induced by it also is easy to regenerate.

It is therefore preferable that reducing the difference of the size changing rate of protective film 13B and the size changing rate of protective film 13A as far as possible. That is, after protective film 13B is saved 100 hours at 80 DEG C of 90%RH, the size changing rate (%) of the longitudinal direction α of film sets For B (α), when the size changing rate (%) of the short side direction β orthogonal with direction α is set as B (β), preferably protective film A and B meet Following formula (5) and (6).

|A(α)-B(α)|≤0.4…(5)

|A(β)-B(β)|≤0.4…(6)

In order to further suppress the curling of polarizing film, preferably | A (α)-B (α) | and | A (β)-B (β) | be respectively 0.2 hereinafter, Particularly preferably zero.

(delay)

Protective film 13B, measurement wavelength 590nm, in the face that measures under conditions of 23 DEG C of 55%RH the delay R0 in direction and The delay Rth of thickness direction can also be set as range same as protective film 13A.

(thickness)

For the thickness of protective film 13B, consider from being thinned polarizing film etc., preferably 10~60 μm, more preferably 15~40 μm.

The solidified material layer 15 of 1-4. active energy ray-curable bonding agent

The solidified material layer 15 of active energy ray-curable bonding agent can be by the solidfied material of active energy ray-curable bonding agent It constitutes.Active energy ray-curable bonding agent can be utilized the radical polymerization mould assembly of optical free radical polymerization active energy ray it is solid Change type bonding agent, be utilized light cationic polymerization cationic polymerization type active energy ray-curable bonding agent or by they The active energy ray-curable bonding agent of combined mixed type.

The active energy ray-curable bonding agent of radical polymerization mould assembly can be to remember in Japanese Unexamined Patent Publication 2008-009329 bulletin What is carried includes the free-radical polymerised compound and not polar functionalities of the polar group containing hydroxyl, carboxyl etc. with special ratios Free-radical polymerised compound composition etc..Free-radical polymerised compound is preferably the olefinic with free redical polymerization The compound of unsaturated bond.Contain tool in the preferred example of the compound of the ethylenic unsaturated bond with free redical polymerization There is the compound of (methyl) acryloyl group.Replace (methyl) third containing N in the example of compound with (methyl) acryloyl group Acrylamide based compound, (methyl) acrylate based compound etc..(methyl) acrylamide means acrylamide or methyl-prop Acrylamide.

The active energy ray-curable bonding agent of cationic polymerization type can be for as in Japanese Unexamined Patent Publication 2011-028234 bulletin Wavelength disclosed, that 380nm long is compared containing (α) cationically polymerizable compound, (β) light cationic polymerization initiator, (γ) Light show maximum absorption light sensitizer and (δ) naphthalene system's light increase sense auxiliary agent each ingredient composition etc..

In these, consider in terms of cementability, durability are good etc., preferably the active energy ray of free radical aggretion type is solid Change type bonding agent.The active energy ray-curable bonding agent of radical polymerization mould assembly contains free-radical polymerised compound and light certainly It, as needed can be further containing light sensitizer etc. by base polymerization initiator.

Free-radical polymerised compound preferably comprises unsaturationization in the molecule with 1 or more ethylenic unsaturated bond Close object.Contain (methyl) acrylic compounds in the example of such unsaturated compound；N- vinyl -2- pyrrolidines Ketone, vinyl hexanediacetate, vinyl compound as decanedioic acid diethyl enester；Triallyl isocyanurate, triallylamine, Four allyl ester of Pyromellitic Acid, N, N, N ', N '-tetraallyl -1,4-Diaminobutane, tetraallyl ammonium salt, allylamine are in this way Allyl compound；Unsaturated carboxylic acid as maleic acid and itaconic acid etc., preferably (methyl) acrylic compounds.

In the example of (methyl) acrylic compounds containing (methyl) esters of acrylic acid, (methyl) acrylic amide, (methyl) acrylic acid, (methyl) acryloyl morpholine, (methyl) methacrylaldehyde etc..

Contain (methyl) methyl acrylate, (methyl) ethyl acrylate, (first in the example of (methyl) esters of acrylic acid Base) (methyl) alkyl-acrylates such as propyl acrylate；(methyl) acrylic acid 2- hydroxy methacrylate, (methyl) acrylic acid 2- hydroxyl Propyl ester etc. (methyl) hydroxyalkyl acrylates class；The alicyclic rings such as (methyl) cyclohexyl acrylate, (methyl) isobornyl acrylate Formula (methyl) esters of acrylic acid；(methyl) benzyl acrylate etc. has (methyl) esters of acrylic acid of aromatic ring；Tripropylene glycol (methyl) esters of acrylic acid of the dihydric alcohols such as diacrylate etc..Contain hydroxyethyl in the example of (methyl) acrylic amide Acrylamide.

Contain in the example of optical free radical polymerization initiator

4 '-phenoxy group -2,2- dichloroacetophenones, 4 '-tert-butyl -2,2- dichloroacetophenones, 2,2- dimethoxy -2- benzene Benzoylformaldoxime, 2- methyl-1-(4- methyl mercapto phenyl)-2- morpholino propane-1- ketone, 1- hydroxycyclohexylphenylketone, α, α-two The acetophenones system Photoepolymerizationinitiater initiaters such as acetophenone, 2- hydroxy-2-methyl -1- phenyl-propane -1- ketone；

Benzoin, benzoin methyl ether, benzoin ether system Photoepolymerizationinitiater initiater as benzoin ethyl ether；Hexichol first Ketone, o- benzoyl methyl benzoate, benzophenone series Photoepolymerizationinitiater initiater as 4- phenyl benzophenone；

Thioxanthones system light as the thioxanthones system such as 2-isopropylthioxanthone, 2,4- diethyl thioxanthone Photoepolymerizationinitiater initiater Polymerization initiator；

Acylphosphine oxide system Photoepolymerizationinitiater initiater etc. as 2,4,6-trimethylbenzoyldiphenylphosphine oxide.

The active energy ray-curable bonding agent of radical polymerization mould assembly can also contain light sensitizer.By increasing sense containing light Agent, reactivity improve, and the mechanical strength of solidfied material, adhesive strength can be made to improve.Light sensitizer can be such as carbonyls, have Organic sulfur compound, persulfide, redox based compound, azo or diazonium compound, halogen compounds, photo-reduction pigment Deng.

Contain benzoin methyl ether, benzoin isopropyl ether, α, alpha, alpha-dimethyl oxygroup-α-phenyl in the example of light sensitizer The benzoin derivatives such as acetophenone；The hexichol of benzophenone, 2,4- dichloro benzophenone, o- benzoyl methyl benzoate etc. Ketone derivatives；The thioxanthone derivates etc. of 2-chlorothioxanthone, 2-isopropylthioxanthone etc..

The thickness of the solidified material layer 15 of active energy ray-curable bonding agent is usually 0.01~10 μm, preferably 0.5~5 μm。

The manufacturing method of 1-5. polarizing film 10

Polarizing film 10 of the invention is by making polarizer 11 and process that protective film 13A or 13B is bonded with bonding agent It makes.Polarizer 11 is bonded the polyethenol series bonding agent that fully saponified type can be used, acetyl second with protective film 13A's or 13B Acyl modified polyethenol series bonding agent, active energy ray-curable bonding agent etc. carry out.In the present invention, from need not use Water and can in the short time by the considerations such as polarizer 11 and protective film 13A or 13B be bonded well, it is preferable to use active-energy Line curability bonding agent.That is, the solidfied material of polaroid protective film and polarizer preferably via active energy ray-curable bonding agent Layer and be bonded.

That is, polarizing film 10 can be manufactured by following processes: 1) to the bonding plane of protective film 13A or 13B and polarizer into The process of row easily bonding processing；2) activity above-mentioned is coated at least one of bonding plane of polarizer and polaroid protective film The process of energy ray-curable bonding agent；3) polarizer 11 is bonded with protective film 13A or 13B via obtained adhesive layer Process；With 4) consolidate adhesive layer in the state of being bonded polarizer 11 with protective film 13A or 13B via adhesive layer The process of change.1) process can be implemented as needed.

In the example of easy bonding processing in above-mentioned process 1), sided corona treatment, corona treatment etc. can be enumerated.

In above-mentioned process 4), active energy ray is irradiated to uncured active energy ray-curable adhesive layer and is made Adhesive layer solidification containing epoxide, oxetane compound.Make as a result, polarizer and polaroid protective film via The solidified material layer of active energy ray-curable bonding agent and be bonded.

As active energy ray, luminous ray, ultraviolet light, X-ray, electron beam etc. can be used, be easy from processing, solidification Speed also fully considers, it is generally preferable that using electron beam or ultraviolet light.

For the irradiation condition of electron beam, as long as the cured condition of bonding agent can be made, then it can be using arbitrary suitable When condition.For example, acceleration voltage is preferably 5~300kV, more preferably 10~250kV for electron beam irradiation.Accelerate In the case that voltage is less than 5kV, it is possible to which electron beam does not reach bonding agent and becomes solidification deficiency, if acceleration voltage is more than 300kV, too strong by the power of impregnation of sample, electron beam is turned back, it is possible to cause to damage to polaroid protective film, polarizer.According to In the range of quantity of X-rays X is 5~100kGy, in the range of more preferably 10~75kGy.In the case that illuminated line amount is less than 5kGy, Bonding agent becomes solidification deficiency, if it exceeds 100kGy, causes to damage, be easy to happen machinery to polaroid protective film, polarizer The decline of intensity, xanthochromia.

For ultraviolet irradiation condition, as long as the cured condition of above-mentioned bonding agent can be made, it can be using any Condition appropriate.Ultraviolet irradiation amount is in terms of accumulated light, preferably 50~1500mJ/cm², more preferably 100~ 500mJ/cm²。

2. liquid crystal display device

Liquid crystal display device of the invention successively contains the first polarizing film, liquid crystal cells, the second polarizing film and backlight.And And it can at least make the second polarizing film or both the first polarizing film and the second polarizing film for polarizing film of the invention.The present invention Polarizing film preferably configured in such a way that protective film A becomes liquid crystal cell side.

Liquid crystal display device of the invention can be the medium-and-large-sized liquid crystal display device such as TV, notebook personal computer； It is also possible to the small-sized liquid crystal display device of smart phone etc..Wherein, consider from being easy to get effect of the invention, it is of the invention Liquid crystal display device be preferably the diagonal direction of the display area (not shown) of smart phone etc. length be 10 inches or less, it is excellent 6 inches of small-sized liquid crystal display devices below of selection of land.

Fig. 2 is the schematic diagram for indicating an example of small-sized liquid crystal display device.As illustrated in fig. 2, small-sized liquid crystal display Device 30 contains liquid crystal cells 50, the first polarizing film 70 for clamping it and the second polarizing film 90 and backlight 110.Small-sized liquid crystal Glass cover-plate 130 that face of the showing device 30 also containing the visible side in the first polarizing film 70 is configured with, the first polarizing film 70 with The touch panel 150 that is configured between liquid crystal cells 50 and the rechargeable battery 170 that is configured with of back side in backlight 110.

The display pattern of liquid crystal cells 50 can be such as STN, TN, OCB, HAN, VA (MVA, PVA), IPS, FFS The various display patterns of (Fringe Field Switching) etc. consider, preferably IPS mode or FFS mould from visual angle is extensively equal Formula.

The face for the visible side that first polarizing film 70 configured in liquid crystal cells 50；It is polarized containing the first polarizer 71, first The protective film 73B (F1) that the face of the opposite side of the liquid crystal cells 50 of mirror 71 is configured with and the liquid crystal cells in the first polarizer 71 The protective film 73A (F2) that the face of 50 sides is configured with.The face for the backlight side that second polarizing film 90 configured in liquid crystal cells 50；Contain It two polarizers 91, the protective film 93A (F3) being configured in the face of 50 side of liquid crystal cells of the second polarizer 91 and is polarized second The protective film 93B (F4) that the face of the opposite side of the liquid crystal cells 50 of mirror 91 is configured with.In Fig. 2, the first polarizing film 70 and second is inclined Both pieces 90 that shakes are polarizing film of the invention；Protective film 73A (F2) and protective film 93A (F3) be protective film A above-mentioned (or protection Film 13A)；The solidified material layer 75 and 95 of active energy ray-curable bonding agent is active energy ray-curable bonding agent above-mentioned Solidified material layer 15.

Touch panel 150 configures between liquid crystal cells 50 and the first polarizing film 70 (On-cell type).But, it touches The position of panel part 150 is not limited to mode shown in Fig. 2, and touch panel 150 can be integrally provided to glass cover-plate 130 (glass cover-plate is one-piece type)；It may also be arranged on the inside (In-cell type) of liquid crystal cells 50.

Rechargeable battery 170 can be for such as lithium ion secondary battery.

In liquid crystal display device, generally, due to the influence of the heat, external environment of backlight, heat, humidity are easily varied.It is special Not, in small-sized liquid crystal display device 30 shown in Fig. 2, exothermic rechargeable battery when due to not only also containing charge and discharge 170, and device volume is also small, therefore heat, moisture are easy to accumulate in the device.Therefore, because the change of heat, humidity in device Change, the first polarizer 71, the second polarizer 91 are also easy to happen change in size.

In the present invention, the size changing rate of protective film 73A (F2) and 93A (F3) are moderately increased.Although as a result, will Protective film 73A (F2) and the solidified material layer 75 of the first polarizer 71 active energy ray-curable bonding agent are be bonded securely, The convergent force to protective film 73A (F2) first polarizer 71 applied can be made relatively to become smaller.Similarly, although by protective film 93A (F3) and the solidified material layer 95 of the second polarizer 91 active energy ray-curable bonding agent are be bonded securely, can also make Relatively become smaller to the convergent force of protective film 93A (F3) second polarizer 91 applied.These as a result, can reduce protective film Deformation in 73A (F2) and 93A (F3) can inhibit deformation optically to generate.

In turn, can make the size changing rate of protective film 73B (F1) and the size changing rate of protective film 73A (F2) difference and The difference of the size changing rate of the size changing rate and protective film 93B (F4) of protective film 93A (F3) is certain following.Thus, it is possible to The curling (warpage) for inhibiting the first polarizing film 70 and the second polarizing film 90 respectively, can further suppress the display being induced by it not .

Embodiment

It is exemplified below embodiment to specifically describe the present invention, but the present invention is not limited to these embodiments.

1. the material of protective film

< cellulose esters >

Cellulose triacetate (degree of substitution with acetyl group 2.85, Mw285000)

< petchem >

[table 3]

< lubricant >

[changing 19]

Lubricant 1:

Lubricant 2:

Lubricant 3:

< high rigidity agent >

[changing 20]

High rigidity agent 1:

High rigidity agent 2:

High rigidity agent 3:

2. the production of polarizing film

(1) production of cellulose ester membrane

101 > of < cellulose ester membrane

Following compositions are put into sealing container, 70 DEG C is heated to, cellulose triacetate is made while stirring fully Dissolution.The time that dissolution needs is 4 hours.Obtained solution is filtered, rubber cement is made.

(composition of rubber cement)

Cellulose triacetate (degree of substitution with acetyl group 2.85, Mw285000): 100 mass parts

Petchem K1:3 mass parts

Methylene chloride: 475 mass parts

Methanol: 50 mass parts

チ ヌ ビ Application 928:2 mass parts

Obtained rubber cement is used into the stainless steel band that 22 DEG C are equably cast to casting device, at 35 DEG C of rubber cement temperature On supporting mass.Then, it after so that the rubber cement on supporting mass is dried to strippable range, removes, obtains from stainless steel band supporting mass Membranoid substance is arrived.The residual solvent amount of rubber cement when removing is 25%.

For obtained membranoid substance, stenter, side under conditions of 125 DEG C of draft temperature, 1.05 times of stretching ratio are used Side is stretched on width direction (direction TD) to make it dry.Then, release width is kept, when being conveyed with multiple rollers at 110 DEG C Lower drying 8 minutes.Make conveyance tension 70N/m.Then, width 10mm is implemented to film both ends, high 5 μm of annular knurl is processed, production The cellulose ester membrane 101 that 25 μm of film thickness.Make film width 1300mm, batch length to be 3000m.Make coiling tension initial stage tension 150N/1300mm, final coiling tension 100N/1300mm.

102~107 > of < cellulose ester membrane

The content for changing petchem K1 like that as shown in table 4, in addition to this makes in the same manner as cellulose ester membrane 101 Cellulose ester membrane 102~107 is made.

108~114 > of < cellulose ester membrane

The content of petchem K1 is become into 12 mass parts, and changes the defeated of membranoid substance like that as shown in table 4 More than one of tension, stretching condition (draft temperature, stretching ratio) and drying condition (drying temperature, drying time) are sent, are removed Cellulose ester membrane 108~114 has been made except this in the same manner as cellulose ester membrane 101.

115~117 > of < cellulose ester membrane

It is added to lubricant shown in table 4, has in addition to this made cellulose ester membrane in the same manner as cellulose ester membrane 111 115~117.

118~120 > of < cellulose ester membrane

Petchem K1 is not added, adds high rigidity agent shown in table 4, and change like that as shown in table 4 Manufacturing condition, has in addition to this made cellulose ester membrane 118~120 in the same manner as cellulose ester membrane 101.

121~123 > of < cellulose ester membrane

The type for changing petchem like that as shown in table 4, in addition to this makes in the same manner as cellulose ester membrane 105 Cellulose ester membrane 121~123 is made.

124 > of < cellulose ester membrane

In turn, following program makings is used referring to the paragraph 0161~0165 of Japanese Unexamined Patent Publication 2008-217022 bulletin It is equivalent to the film of the hyaline membrane 104 of the bulletin.

Following compositions are dissolved, Cellulose acylate solutions have been obtained.

(Cellulose acylate solutions composition)

Cellulose triacetate Ce-1 (degree of substitution with acetyl group 2.94): 100 mass parts

Methylene chloride: 480.0 mass parts

Methanol: 71.7 mass parts

The silicon dioxide granule dispersion liquid of average grain diameter 16nm: 0.15 mass parts

Reduce optically anisotropic compound A-19 (KI): 9.0 mass parts

Wavelength dispersion regulator UV-105 (HB): 0.1 mass parts

Citrate mixture (citric acid, mono ethyl ester, diethylester, triethyl mixture): 0.01 mass parts

[changing 21]

Above-mentioned Cellulose acylate solutions are cast using band casting machine.Film is removed from band under residual solvent amount 30%, It is 40 minutes dry at 130 DEG C when being conveyed by conveying roller, manufacture cellulose acylate film 124.Make conveyance tension 100N/ m.The residual solvent amount of obtained cellulose acylate film is 0.1%, and film thickness is 80 μm.

The size changing rate (direction MD, TD) of the cellulose ester membrane measured using the following method, phase difference (Ro, ) and mist degree Rth.

(size changing rate)

1) size that obtained film is cut out to 10cm × 10cm, is made sample film.In the direction MD (direction β) of the sample film On marked at a distance of 2 points of 100mm.Similarly, in phase on the TD direction (direction α) orthogonal with the direction MD of sample film 2 points away from 100mm mark.After the film has been stood 24 hours at 23 DEG C of 55%RH, all directions are measured respectively between 2 points Distance D0.

2) then, which is saved 100 hours in the baking oven of 80 DEG C of 90%RH.Then, it is taken out from baking oven, at 23 DEG C After 55%RH relative humidity 24 hours, each all directions measure the distance D1 between 2 points marked respectively.

3) then, above-mentioned measured value D0 1) and above-mentioned measured value D1 2) is substituted into following formula, is calculated in an oven Save the ratio (%) of the change in size of front and back.Value, which becomes negative, indicates that film is shunk.

Ratio (%)=(D1-D0)/D0 × 100 of change in size

(phase difference R₀、Rth)

1) to obtained film in 23 DEG C of 55%RH relative humidities.The mean refraction of the film after damping is measured with Abbe refractometer etc. Rate.

2) measuring (strain) measurement with KOBRA21ADH, prince makes to measure wavelength 590nm with the normal parallel of the film surface R of light when being incident on the film after damping₀。

3) KOBRA21ADH is used to measure using the slow axis in the face of film as sloping shaft (rotary shaft), relative to film surface Normal makes the length of delay R (θ) when measuring the light incidence of wavelength 590nm from the angle (incidence angle (θ)) of θ.The survey of length of delay R (θ) Surely every 10 ° of 6 points of the progress of the range that can be 0 °~50 ° in θ.Slow axis in the face of film is confirmed using KOBRA21ADH.

4) R by determining₀With R (θ) and mean refractive index above-mentioned and film thickness, using KOBRA21ADH calculate nx, Ny and nz calculates the Rth under measurement wavelength 590nm.The measurement of delay carries out under the conditions of 23 DEG C of 55%RH.

(mist degree)

Obtained film is cut out into 5cm square and sample film is made.According to JIS K-7136, use haze meter (nephelometer) (model: NDH 2000, the electric color (strain) of Japan manufacture) measures the mist degree of the sample film.

By obtained film 101~123 evaluation result is shown in table in 4.

As shown in table 4 like that, it is known that in the film 102~106 that defined range contains petchem be all that can make 80 Size changing rate under DEG C 90%RH is moderately big and phase difference (particularly Rth) can be made also to reduce.On the other hand, it is known that poly- The size changing rate of the very few film 101 of the content of ester compounds is excessive, and phase difference is excessive.In addition, knowing containing for petchem The internal haze for measuring excessive film 107 rises.

By the comparison of film 108 and 109 or the comparison of film 110~112, it is known that by making conveyance tension, stretching ratio and temperature Degree is all low, and the size changing rate (direction MD, the direction TD) of the film made becomes larger.In addition, by the comparison of film 113 and 114, it is known that By reducing drying temperature, the size changing rate (direction MD, the direction TD) of obtained film becomes larger.

By the comparison of film 111 and 115~117, it is known that by further adding lubricant, the mist for the film that can be reduced Degree.It is thought that because are as follows: since the sliding property of the film containing lubricant is good, even if conveyance tension is small, also it is not susceptible to With the poor contact of conveying roller, as a result, the film containing lubricant can inhibit to damage film surface caused external mist degree Increase.

By the comparison of film 105,121 and 122 and film 123, it is known that used petchem K1, K6 without aromatic rings and The film 105,121 and 122 of K5 is compared with the film 123 for having used the petchem K14 containing aromatic rings, size changing rate appropriateness Ground is high.

The size changing rate with the comparable film 124 of the embodiment of patent document 1 is determined with said determination method, as a result may be used Know: the size changing rate in the direction MD is that the size changing rate in the direction -0.05%, TD is -0.05%, significantly small.

The production > of < polarizer

It is swollen thick 30 μm of polyvinyl alcohol film in 35 DEG C of water.By obtained film by iodine 0.075g, potassium iodide 5g It is impregnated 60 seconds in the aqueous solution of water 100g composition, and then is impregnated in 45 be made of potassium iodide 3g, boric acid 7.5g and water 100g DEG C aqueous solution.Obtained film is uniaxially stretched under conditions of 55 DEG C of draft temperature, 3 times of stretching ratio.This is uniaxially stretched Film water washes rear, drying, has obtained 5 μm of thickness of polarizer.Similarly, thickness, the stretching condition for adjusting master film, make respectively The polarizer that 2 μm, 3 μm, 10 μm, 15 μm and 20 μm of thickness.

The production > of < polarizing film

(embodiment 1)

1) preparation (radical polymerization mould assembly) of active energy ray-curable bonding agent liquid 1

Deaeration after following each ingredients is mixed, prepares the active energy ray-curable bonding agent liquid 1 of radical polymerization mould assembly.

(active energy ray-curable bonding agent liquid 1)

Free-radical polymerised compound 1: hydroxyethyl acrylamide (HEAA, Tg123 DEG C of homopolymer, emerging people's corporation Make): 39.1 mass %

Free-radical polymerised compound 2: the tripropylene glycol diacrylate (Tg69 of ア ロ ニ ッ Network ス M-220, homopolymer DEG C, East Asia Synesis Company manufacture): 19.0 mass %

Free-radical polymerised compound 3: acryloyl morpholine (ACMO, Tg150 DEG C of homopolymer, the manufacture of Xing Ren company): 39.1 quality %

Radical polymerization initiator 1: diethyl thioxanthone (KAYACURE DETX-S, Japanese chemical drug corporation are made): 1.4 Quality %

Radical polymerization initiator 2:2- methyl-1-(4- methyl mercapto phenyl)-2- morpholino propane-1- ketone (IRGACURE907, BASF AG's manufacture): 1.4 mass %

2) production of polarizing film

Firstly, preparing the above-mentioned film 102 made as protective film A, implementing Corona discharge Treatment to its surface.Electricity The condition of corona processing is set as corona output intensity 2.0kW, linear velocity 18m/ minutes.Then, at the corona discharge of the film Reason face with rod coaters be respectively coated above-mentioned preparation radical polymerization mould assembly active energy ray-curable bonding agent liquid 1 so that solidification Film thickness afterwards becomes about 3 μm, forms active energy ray-curable adhesive layer.In obtained active energy ray-curable bonding 5 μm of thickness of polarizer of above-mentioned production is bonded by oxidant layer.

Then, as protective film B, prepare the above-mentioned film 102 made, to its surface under the conditions of with aforementioned same Implement Corona discharge Treatment.Then, the freedom of above-mentioned preparation is coated in the same manner as aforementioned in the Corona discharge Treatment face of the film The active energy ray-curable bonding agent liquid 1 of base aggretion type, forms active energy ray-curable adhesive layer.

Fitting has the polarizer of film 102 on the active energy ray-curable adhesive layer, has obtained (protecting film 102 Cuticula A)/active energy ray-curable adhesive layer/polarizer/active energy ray-curable adhesive layer/102 (protective film of film B the sandwich) being laminated.

To the one side of the sandwich, ultraviolet lamp (the Fusion UV for having band conveyer is used The Light HAMMER10 valve of Systems, Inc company manufacture: V-shaped valve, peak illumination: 1600mW/cm²) irradiation ultraviolet light (envelope Enter the metal halide lamp of gallium) so that cumulative exposure becomes 1000/mJ/cm²(380~440nm of wavelength), makes active energy ray The solidification of curing type adhesive layer, has obtained polarizing film 202.

(embodiment 2~13 and 29~31, the Comparative Examples 1 to 5)

Other than changing protective film A and B as shown in table 5 or table 7, polarized similarly to Example 1 Piece 201,203~217 and 233~236.

(embodiment 14~18)

The thickness for changing polarizer like that as shown in table 6, has in addition to this obtained polarizing film similarly to Example 8 218~222.

(embodiment 19)

The preparation of active energy ray-curable bonding agent liquid 2 (cationic polymerization type)

Deaeration after following each ingredients is mixed, prepares active energy ray-curable bonding agent liquid 2.It should be noted that three virtues Base sulfonium hexafluorophosphate cooperates as 50% polypropylene carbonate ester solution, it is following it is middle indicate triaryl matte hexafluorophosphates solids at Component.

(active energy ray-curable bonding agent liquid 2)

3,4- epoxycyclohexyl-methyl -3,4- epoxycyclohexane carboxylates: 45 mass parts

エ ポ リ ー De GT-301 (alicyclic epoxy resin of ダ イ セ Le chemical company manufacture): 40 mass parts

1,4-butanediol diglycidyl ether: 15 mass parts

Triaryl matte hexafluorophosphate: 2.3 mass parts

9,10- dibutoxy anthracenes: 0.1 mass parts

Isosorbide-5-Nitrae-diethoxy naphthalene: 2.0 mass parts

In the same manner as aforementioned, as protective film A and protective film B, the film 111 of above-mentioned production is prepared respectively, to its surface Implement Corona discharge Treatment.Then, oneself of above-mentioned preparation is respectively coated using rod coaters in the Corona discharge Treatment face of the film By the active energy ray-curable bonding agent liquid 2 of base aggretion type so that the film thickness after solidifying becomes about 3 μm, active-energy is formd Line curing type adhesive layer.Then, obtained by film 111 (protective film A)/active energy ray-curable adhesive layer/polarizer/ The sandwich that active energy ray-curable adhesive layer/film 111 (protective film B) has been laminated.

To the one side of the sandwich, ultraviolet lamp (the Fusion UV for having band conveyer is used The Light HAMMER10 valve of Systems, Inc company manufacture: V-shaped valve) irradiation ultraviolet light (metal halide lamp of enclosed gallium) So that cumulative exposure becomes 750/mJ/cm²(380~440nm of wavelength) solidifies active energy ray-curable adhesive layer, Polarizing film 223 is obtained.

(embodiment 20~25)

The type for changing protective film B like that as shown in table 6, has in addition to this obtained polarizing film similarly to Example 8 224~229.

(embodiment 26~28)

Other than the type for changing protective film B like that as shown in table 6, in addition to this obtain similarly to Example 17 partially Shake piece 230~232.

The presence or absence of the curling of polarizing film being had rated with the following method.

(curling of polarizing film)

The size that polarizing film is cut out to 100mm × 100mm, as polarizing film sample.By obtained polarizing film sample 80 After being saved 300 hours in the environment of DEG C 90%RH, under polarizing film sample being stood in the plane so that protective film A is.Then, 4 jiaos of the height apart from plane for measuring polarizing film sample, calculates their average value, as " value of curling ".

◎: the height of the part of warpage is less than 2mm

Zero: the height of the part of warpage is 2mm or more and less than 4mm

△: the height of the part of warpage is 4mm or more and less than 6mm

×: the height of the part of warpage is 6mm or more

In turn, using obtained polarizing film, liquid crystal display device is made with the following method, it is uneven to have rated display.

(display is uneven)

1) production of display device

The IPS mode LCD that diagonal length as display area is 4 inches prepares Apple Inc.'s manufacture I-phone5s is removed from it by two polarizing films.Then, it is (same to prepare two polarizing films made under same manufacturing condition The polarizing film of one serial number), it is shown one of wherein the two sides of the one-piece type liquid crystal cells of touch panel is fitted in respectively Showing device.For fitting, configured in such a way that the protective film A of polarizing film is contacted with liquid crystal cells respectively.So that polarizing film Absorption axiss and the absorption axiss of the polarizing film pasted in advance become same direction.

2) it evaluates

With the display unevenness for the display device that the following method has rated.

That is, obtained display device is saved 3 hours under conditions of 50 DEG C of 80%RH.Then, by display device 23 Saved in the darkroom of DEG C 80%RH after a certain period of time, to the color (of picture when it being made to carry out black display ) homogeneity carry out Sense evaluation.

◎: unevenness is not found in entire surface

Zero: slightly unevenness, but be in allowing on practical

△: it can be seen that uneven, worry

×: it is clearly observed unevenness

By embodiment 1~13 and the Comparative Examples 1 to 5 evaluation result is shown in table 5；The evaluation result of embodiment 14~28 is shown In table 6；By embodiment 29~31 evaluation result is shown in table 7.

As shown in table 5~7, it is known that the size changing rate of protective film A (F2 or F3) is -0.3%~-1.5% The display device of the Examples 1 to 31 of range is all that display is uneven few, visual good.In addition we know, Examples 1 to 28 is inclined The curling of vibration piece is also few.

In contrast, for the display device of the too small comparative example 3 of the size changing rate of protective film A (F2 or F3), it can Know that display is uneven big.It is thought that due to: because polarizer and protective film A (F2 or F3) is be bonded with active energy ray-curable Agent is bonded securely, therefore is significantly produced optical deformation (birefringent) by the convergent force of polarizer.

On the other hand, it is known that the display device of the excessive comparative example 1 and 4 of the size changing rate of protective film A (F2 or F3) It is that display is uneven big.It is thought that due to: because the size changing rate of protective film is excessive, produces and be not required in protective film That wants is birefringent.In addition, a little curling has occurred in the polarizing film of comparative example 1 and 4.It is thought that due to: the size of protective film A becomes Rate is excessive, and deformation is produced between the glass substrate of liquid crystal cells.

It is uneven that display is produced in the display device of comparative example 2, it is believed that be the polyesterification because in protective film A (F2 or F3) The content for closing object is excessive, equably not compatible with cellulose esters, and internal haze rises.In addition, the display device of comparative example 2 Contrast is also low.

In turn, it is known that used the display device of the comparative example 5 of film 124 to generate display uneven.It is thought that being drawn by following It rises: since the size changing rate of film 124 is too small, the display unevenness for mainly originating from optical skew has occurred.

Even if in embodiment, the embodiment that the absolute value of the size changing rate of protective film A (F2 or F3) is 0.5% or more 7 display device is compared with the display device of embodiment 6 of the absolute value of size changing rate less than 0.5%, it is known that visual special It is not good.

In addition, as shown in table 7 like that it is found that the petchem in protective film A (F2 or F3) is free of the reality of aromatic rings The display for the embodiment 31 that the display device and the petchem in protective film A (F2 or F3) for applying example 4 and 29 contain aromatic rings The display device of the big embodiment 30 of molecular weight of device, petchem is compared, and is shown uneven few.It thereby implies that without fragrance Ring and molecular weight are certain petchem below and are more than a certain amount of petchem containing aromatic rings, molecular weight It compares, is easy moderately to improve the size changing rate of protective film A.

And then it is found that polarizer with a thickness of the display device of 15 μm of embodiments 15~17 below and the thickness of polarizer Display device for 20 μm of embodiment 18 is compared, visual good.Speculate this is because being risen if the thickness of polarizer is small The convergent force of polariscope also becomes smaller, and the deformation generated in protective film is also few.Polarizer fills with a thickness of the display of 2 μm of embodiment 14 Setting the low supposition of middle visuality is because due to deteriorating polarizer through moisture etc..

In turn, the display device of embodiment 25 does not find unevenness in the central portion of display picture, but in display picture Observe light quantity unevenness in end.It is thought that observing the light for not being due to protective film A in the display device of embodiment 25 The unevenness of deformation, but observe the unevenness of the curling due to polarizing film.

And then it is found that the difference of the size changing rate of protective film A and B is 0.34% embodiment 22~23 and 26~28 below Polarizing film with the difference of size changing rate be 0.4% or more embodiment 20~21 and 24~25 polarizing film compared with, Ke Yiliang Inhibit to crimp well.

The application is claimed priority based on Japanese Patent Application 2014-041830 filed on March 4th, 2014.It is said in this application The content recorded in bright book and attached drawing is all applied in present specification.

Industrial availability

According to the present invention it is possible to provide polarizing film, being will be by polarizer and protective film via active energy ray-curable The polarizing film that adhesive layer has been bonded can inhibit the visual decline of liquid crystal display device.

The explanation of symbol

1 liquid crystal display device

3,50 liquid crystal cells

5,70 first polarizing film

5-1,71 first polarizers

5-3A, 7-3A, 73A, 93A protective film A

5-3B, 7-3B, 73B, 93B protective film B

7,90 second polarizing film

7-1,91 second polarizers

10 polarizing films

11 polarizers

13A protective film A

13B protective film B

15, the solidified material layer of 75,95 active energy ray-curable bonding agents

30 small-sized liquid crystal display devices

110 backlights

130 glass cover-plates

150 touch panels

170 rechargeable batteries

Claims (9)

1. a kind of manufacturing method of polarizing film, it includes:

1) prepare the process of protective film A, wherein after saving 100 hours at 80 DEG C of 90%RH, the longitudinal direction α of film Size changing rate (%) is set as A (α), and the size changing rate (%) of the short side direction β orthogonal with the longitudinal direction α is set as A When (β), the protective film A meets following formula (1) and (2):

-1.5≤A(α)≤-0.3…(1)

- 1.5≤A (β)≤- 0.3 ... (2),

2) process for obtaining sandwich, the sandwich contain polarizer, the polarizer one side it is solid via active energy ray Change type adhesive layer and the protective film A that has been laminated and the polarizer another side via active energy ray-curable Adhesive layer and the protective film B being configured with；With

3) active energy ray is irradiated to the sandwich and makes the active energy ray-curable adhesive layer solidification to obtain partially Shake piece process, the polarizing film contain the polarizer, the polarizer one side via the active energy line curing The solidified material layer of type bonding agent and the protective film A that configures and the polarizer another side via the active-energy The solidified material layer of line curing type bonding agent and the protective film B configured,

1) process for preparing protective film A includes:

The process for 1A) obtaining membranoid substance, the membranoid substance contain cellulose esters and carry out glycol and dicarboxylic acids obtained from polycondensation Petchem, and relative to the cellulose esters, the content of the petchem is 5~30 mass %；

1B) 110~135 DEG C at a temperature of, with 1.03~1.06 times of stretching ratio by the membranoid substance width direction into The process that row stretches；With

1C) on one side the tension with 70~80N/m convey film obtained from described stretched, while exist 100~120 DEG C of temperature The process of lower drying 5~10 minutes.

2. the manufacturing method of polarizing film described in claim 1, wherein the petchem is to make selected from by aliphatic dicarboxyl Acid and ester ring type dicarboxylic acids in dicarboxylic acids in the group being made of aliphatic diol, alkyl ether glycol and ester ring type glycol Glycol carry out polycondensation obtained from compound.

3. the manufacturing method of polarizing film of any of claims 1 or 2, wherein the protective film A meets following formula (3) and (4):

- 1.5≤A (α) < -0.5 ... (3)

- 1.5≤A (β) < -0.5 ... (4).

4. the manufacturing method of polarizing film of any of claims 1 or 2, wherein save the protective film B at 80 DEG C of 90%RH The size changing rate (%) of after 100 hours, film longitudinal direction α is set as B (α), will be orthogonal relative to the longitudinal direction α When the size changing rate (%) of short side direction β is set as B (β), the protective film A and B meets following formula (5) and (6):

|A(α)-B(α)|≤0.4…(5)

|A(β)-B(β)|≤0.4…(6)。

5. the manufacturing method of polarizing film of any of claims 1 or 2, wherein the polarizer with a thickness of 3~15 μm.

6. the manufacturing method of polarizing film of any of claims 1 or 2, wherein the protective film A will be defined by following formula (I)s, And the delay in direction is set as Ro (590) in the face measured in the case where measuring wavelength 590nm, will be defined and surveyed by following formula (II)s When the delay of the thickness direction measured under the long 590nm of standing wave is set as (590) Rth, meet | Ro (590) |≤10nm, | Rth (590) |≤10nm,

Formula (I) Ro=(nx-ny) × t (nm)

Formula (II) Rth={ (nx+ny)/2-nz } × t (nm)

In formula (I) and (II),

Nx indicates that direction refractive index is as the refractive index on maximum slow axis direction x in the face of film；

Ny indicates the refractive index on the direction y that direction is orthogonal with the slow axis direction x in the face of film；

Nz indicates the refractive index of the thickness direction z of film；

The thickness of t (nm) expression film.

7. the manufacturing method of polarizing film of any of claims 1 or 2, wherein the protective film A also contains lubricant.

8. the manufacturing method of polarizing film of any of claims 1 or 2, wherein the protective film B also contains high rigidity agent.

9. the manufacturing method of polarizing film of any of claims 1 or 2, wherein the protective film A with a thickness of 10~60 μm.